CN110746907B - Hot-melt pressure-sensitive adhesive suitable for bonding polyolefin woven cloth and metal plate and preparation method thereof - Google Patents

Abstract

The invention discloses a hot-melt pressure-sensitive adhesive suitable for bonding polyolefin woven cloth and a metal plate, which is prepared from the following raw materials in parts by weight: 15-25 parts of thermoplastic elastomer polymer, 0.5-1.5 parts of maleic anhydride, 0.2-0.4 part of dicumyl peroxide, 35-45 parts of tackifying resin, 35-45 parts of plasticizer, 0.5-1 part of antioxidant and 1-2 parts of cross-linking agent; the invention also discloses a preparation method of the hot-melt pressure-sensitive adhesive. The hot-melt pressure-sensitive adhesive disclosed by the invention is simple in production process, has better cohesion and initial viscosity, good permanent adhesion and good high-temperature resistance, and can be used for bonding polyolefin woven cloth and metal plates, and particularly has good effect on bonding polyethylene woven cloth and metal plates.

Description

Hot-melt pressure-sensitive adhesive suitable for bonding polyolefin woven cloth and metal plate and preparation method thereof

Technical Field

The invention belongs to the technical field of adhesives, and particularly relates to a hot-melt pressure-sensitive adhesive suitable for bonding polyolefin woven cloth and a metal plate and a preparation method thereof.

Background

Pressure Sensitive Adhesive (PSA) is a self-Adhesive substance which forms a relatively strong bond with relatively little force. The adhesive force formed by the pressure-sensitive adhesive between the surfaces of two objects is mainly Van der Waals force, and the structure of the adhesive surface is not damaged after the adhesive surface is formed. Because it is convenient to use, generally does not influence the surface of the adherend after uncovering, therefore use very extensively.

In recent years, scientific technology is increasingly developed to develop the pressure-sensitive adhesive at home and abroad rapidly. The pressure-sensitive adhesive is available in the forms of solvent, emulsion, hot melt, etc. The Hot Melt Pressure Sensitive Adhesive (HMPSA) is a third generation pressure sensitive adhesive product following solvent type and emulsion type pressure sensitive adhesives, does not contain organic solvent, has no pollution, simple production process, lower cost and convenient use, and is more beneficial to environmental protection and safe production. The hot-melt pressure-sensitive adhesive has double characteristics of hot melting and pressure sensitivity, can be changed into a liquid state when heated to 160-200 ℃, can be coated and used by various methods such as spraying, roller coating, blade coating and the like, is in a solid state when cooled to room temperature, and can generate a good bonding effect by giving a certain pressure.

The traditional hot-melt pressure-sensitive adhesive is usually coated on paper, plastic films, fabrics or metal foils to prepare adhesive tapes or films, is mainly used for various box sealing, box sealing and paper product packaging, label and label sticking and solid part sticking, but has poor sticking effect on difficult-to-stick polyolefin materials and poor high temperature resistance.

Disclosure of Invention

In order to solve the technical problems of low bonding strength and poor high temperature resistance of common hot melt pressure sensitive adhesive products to polyolefin woven materials and metal plates, the invention provides a hot melt pressure sensitive adhesive suitable for bonding polyolefin woven cloth and metal plates, which has a light cross-linking structure and better cohesion and high temperature bonding stability.

The invention also provides a preparation method of the hot-melt pressure-sensitive adhesive suitable for bonding the polyolefin woven cloth and the metal plate.

In order to achieve the purpose, the invention adopts the technical scheme that:

the hot-melt pressure-sensitive adhesive suitable for bonding the polyolefin woven cloth and the metal plate is prepared from the following raw materials in parts by weight: 15-25 parts of thermoplastic elastomer polymer, 0.5-1.5 parts of maleic anhydride, 0.2-0.4 part of dicumyl peroxide, 35-45 parts of tackifying resin, 35-45 parts of plasticizer, 0.5-1 part of antioxidant and 1-2 parts of cross-linking agent.

Preferably, the thermoplastic elastomer polymer is styrene-isoprene-styrene block copolymer (SIS), and the thermoplastic elastomer is grafted with maleic anhydride in the presence of dicumyl peroxide to introduce a crosslinking group.

Preferably, the tackifying resin is one or more selected from petroleum resin, terpene phenolic resin, rosin ester and rosin.

Preferably, the plasticizer is liquid polyisobutene with the molecular weight of 500-2000.

Preferably, the antioxidant is compounded by antioxidant 1010 and antioxidant DLTDP.

Preferably, the crosslinking agent is a liquid bisphenol a type epoxy resin.

The preparation method of the hot-melt pressure-sensitive adhesive comprises the following steps:

(1) weighing the raw materials in parts by weight;

(2) uniformly mixing the thermoplastic elastomer polymer, maleic anhydride and dicumyl peroxide, adding the mixture into a reaction type double-screw extruder preheated to 180-200 ℃, and carrying out extrusion grafting reaction at 180-200 ℃ to obtain a graft type thermoplastic elastomer polymer;

(3) adding the grafted thermoplastic elastomer polymer obtained in the step (2) into a reaction kettle at the temperature of 160-; adding the cross-linking agent, continuing stirring for 15-25 minutes, and cooling to room temperature to obtain the product.

The main polymer thermoplastic elastomer polymer is styrene-isoprene-styrene block copolymer (SIS), has good thermal stability, light glue color, transparency and low melt viscosity, and can bond difficult-to-bond materials such as polyethylene, polypropylene and the like.

In order to obtain better cohesive strength and solve the problem of low bonding strength at high temperature, the invention adopts the high-temperature grafting of polar group maleic anhydride on the main polymer, thereby not only improving the polarity of the main polymer and the bonding strength on metal materials, but also introducing crosslinking points in a molecular chain, forming a slight crosslinking structure in the main polymer through the crosslinking reaction with epoxy resin, obviously improving the cohesion of the hot-melt pressure-sensitive adhesive, improving the high-temperature resistance of the adhesive and improving the service temperature range of the adhesive.

In order to reduce the viscosity, wettability and glass transition temperature of the system and improve the elongation of the hot melt adhesive, so that the adhesive film has low-temperature flexibility and good sealing effect, polyisobutylene with the molecular weight of 500-2000 is selected as a plasticizer. The polyisobutylene is colorless transparent high-viscosity liquid, is aging-resistant, oxidation-resistant and low-temperature-resistant, has self-adhesion, is not easy to migrate and precipitate in a hot melt adhesive system due to high molecular weight, and has good compatibility with a main polymer.

In order to improve the aging of products in the high-temperature processing and using processes, the adoption of a composite antioxidant and a heat stabilizer is necessary. Experiments prove that the anti-aging performance is best when the ratio of the composite antioxidant 1010 to the DLTDP is 1: 1.

In order to improve the initial adhesion of the hot-melt adhesive and improve the wetting capacity of the adhesive to an adherend, tackifying resins (such as C5 petroleum resin, rosin resin and the like) are added to increase the viscoelasticity and the adhesion to a metal plate of the hot-melt adhesive.

In the process of preparing the hot-melt pressure-sensitive adhesive, a double-screw extruder is firstly adopted to carry out high-temperature grafting modification on a thermoplastic elastomer polymer, maleic anhydride and dicumyl peroxide, and then a plasticizer, an antioxidant and tackifying resin are added, so that the purposes are as follows: the main polymer SIS has high melt viscosity, can be efficiently subjected to grafting reaction with maleic anhydride under the conditions of high temperature and high shear, ensures higher grafting rate and uniformity, and can be directly used without further treatment. And because the production site carries out grafting reaction, granulation is not needed, and the grafting reaction product is directly put into a hot melt adhesive mixing kettle for producing the hot melt adhesive, so that the energy consumption can be greatly reduced, the influence on the environment is reduced, the mixing time is shortened, and the production cost is saved.

Compared with the prior art, the invention has the beneficial effects that the prepared hot-melt pressure-sensitive adhesive has the following advantages: 1) the product has high cohesive strength and good initial viscosity; 2) the product has good high-temperature bonding stability; 3) the product has good effect of bonding the polyethylene composite woven material and the metal plate; 4) the production process is simple; 5) no harmful substance is discharged in the production, no solvent is used, and the method belongs to an environment-friendly product.

Detailed Description

In order to make the technical purpose, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention are further described with reference to specific examples, which are intended to explain the present invention and are not to be construed as limiting the present invention, and those who do not specify a specific technique or condition in the examples follow the techniques or conditions described in the literature in the art or follow the product specification.

In the examples described below, thermoplastic elastomer (SIS) is available from Zhongpetrochemical Balin petrochemical company, maleic anhydride is available from Clamayian Fine chemical, Inc., dicumyl peroxide is available from Nanjing Manual chemical technology, Inc., C5 petroleum resin is available from Puyang san Seng chemical, Inc., rosin resin is available from Guangxi Ningming rosin, Inc., plasticizer (liquid polyisobutylene, PIB-JX 6130) is available from Jinjingang lubricating oil additives, Inc., antioxidant (antioxidant 1010 and antioxidant DLTDP) is available from Tianjin Lisheng chemical, Inc., and crosslinking agent (liquid bisphenol A epoxy resin, E44) is available from Zhongpetrochemical Balin petrochemical company. The test method of the peeling strength adopts the experimental methods in GB/T328.20-2007 and GB/T328.23-2007, and a tensile machine used in the test is a microcomputer-controlled electronic universal tester with the model number of CMT 6104.

Example 1

The hot-melt pressure-sensitive adhesive suitable for bonding the polyolefin woven cloth and the metal plate is prepared from the following raw materials in parts by weight: 150 kg of thermoplastic elastomer polymer, 5 kg of maleic anhydride, 2 kg of dicumyl peroxide, 200 kg of C5 petroleum resin, 250 kg of rosin resin, 450 kg of liquid polyisobutylene, 5 kg of antioxidant 1010, 5 kg of antioxidant DLTDP and 20 kg of liquid bisphenol A epoxy resin.

The preparation method of the hot-melt pressure-sensitive adhesive comprises the following steps:

(1) weighing the raw materials in parts by weight;

(2) uniformly mixing a thermoplastic elastomer polymer, maleic anhydride and dicumyl peroxide, adding the mixture into a JSH-D-50 reaction type double-screw extruder (the retention time is 1-1.5 minutes) preheated to 190 ℃, and performing melt extrusion (grafting reaction) at 190 ℃ to obtain a graft type thermoplastic elastomer polymer;

(3) directly flowing the grafted thermoplastic elastomer polymer obtained in the step (2) into an electric heating reaction kettle (volume 1500L) with nitrogen protection and preheating to 180 ℃, and then slowly adding liquid polyisobutylene, an antioxidant 1010, an antioxidant DLTDP, C5 petroleum resin and rosin resin; keeping the temperature in the kettle at 180 ℃ for 60 min; and adding liquid bisphenol A epoxy resin, continuously stirring at 180 ℃ for 20 min to form molten viscous liquid, and cooling to room temperature to obtain the bisphenol A epoxy resin.

Example 2

The hot-melt pressure-sensitive adhesive suitable for bonding the polyolefin woven cloth and the metal plate is prepared from the following raw materials in parts by weight: 180 kg of thermoplastic elastomer polymer, 7 kg of maleic anhydride, 2 kg of dicumyl peroxide, 150 kg of C5 petroleum resin, 270 kg of rosin resin, 380 kg of liquid polyisobutylene, 2.5 kg of antioxidant 1010 and 2.5 kg of antioxidant DLTDP, and 13 kg of liquid bisphenol A epoxy resin.

Example 3

The hot-melt pressure-sensitive adhesive suitable for bonding the polyolefin woven cloth and the metal plate is prepared from the following raw materials in parts by weight: 210 kg of thermoplastic elastomer polymer, 10 kg of maleic anhydride, 3 kg of dicumyl peroxide, 280 kg of C5 petroleum resin, 100 kg of rosin resin, 420 kg of liquid polyisobutylene, 4 kg of antioxidant 1010, 4 kg of antioxidant DLTDP and 16 kg of liquid bisphenol A epoxy resin.

Example 4

The hot-melt pressure-sensitive adhesive suitable for bonding the polyolefin woven cloth and the metal plate is prepared from the following raw materials in parts by weight: 250 kg of thermoplastic elastomer polymer, 15 kg of maleic anhydride, 4 kg of dicumyl peroxide, 200 kg of C5 petroleum resin, 150 kg of rosin resin, 350 kg of liquid polyisobutylene, 2.5 kg of antioxidant 1010 and 2.5 kg of antioxidant DLTDP, and 10 kg of liquid bisphenol A epoxy resin.

The hot melt pressure sensitive adhesives described in examples 2-4 were all prepared according to the method of example 1.

Comparative example 1

A hot-melt pressure-sensitive adhesive is prepared from the following raw materials in parts by weight: 150 kg of thermoplastic elastomer polymer, 200 kg of C5 petroleum resin, 250 kg of rosin resin, 450 kg of liquid polyisobutylene, 5 kg of antioxidant 1010 and 5 kg of antioxidant DLTDP.

The preparation method of the hot-melt pressure-sensitive adhesive comprises the following steps:

(1) weighing the raw materials in parts by weight;

(2) adding a thermoplastic elastomer polymer into a JSH-D-50 reaction type double-screw extruder preheated to 190 ℃, and performing melt extrusion at 190 ℃;

(3) directly flowing the product obtained in the step (2) into an electric heating reaction kettle (volume 1500L) with nitrogen protection and preheating to 180 ℃, and then slowly adding liquid polyisobutylene, an antioxidant 1010, an antioxidant DLTDP, C5 petroleum resin and rosin resin; keeping the temperature in the kettle at 180 ℃ for 60 min; and adding liquid bisphenol A epoxy resin, continuously stirring at 180 ℃ for 20 min to form molten viscous liquid, and cooling to room temperature to obtain the bisphenol A epoxy resin.

The hot-melt pressure-sensitive adhesive is used for bonding the high-density polyethylene (HDPE) composite woven cloth and the galvanized plate to test the bonding performance of the hot-melt pressure-sensitive adhesive. When the hot melt pressure sensitive adhesive obtained in the examples 1 to 4 and the comparative example 1 is used, the hot melt pressure sensitive adhesive is heated and melted, and is coated on the high-density polyethylene composite woven cloth through a casting coating head, and the thickness of the hot melt pressure sensitive adhesive is about 0.5 mm. The test results are shown in Table 1.

TABLE 1 comparison of the Hot melt pressure sensitive adhesive Performance of the examples with that of the comparative example

As can be seen from Table 1, the hot melt pressure sensitive adhesive of the invention has good permanent adhesion and good high temperature resistance, and is suitable for the adhesion of difficult-to-adhere polyolefin woven materials and metal plates.

Claims (5)

1. The hot-melt pressure-sensitive adhesive is suitable for bonding polyolefin woven cloth and a metal plate, and is characterized in that: the feed is prepared from the following raw materials in parts by weight: 15-25 parts of thermoplastic elastomer polymer, 0.5-1.5 parts of maleic anhydride, 0.2-0.4 part of dicumyl peroxide, 35-45 parts of tackifying resin, 35-45 parts of plasticizer, 0.5-1 part of antioxidant and 1-2 parts of cross-linking agent;

the thermoplastic elastomer polymer is a styrene-isoprene-styrene block copolymer, and the thermoplastic elastomer and maleic anhydride are subjected to a grafting reaction in the presence of dicumyl peroxide to introduce a crosslinking group;

the preparation method of the hot-melt pressure-sensitive adhesive comprises the following steps:

(1) weighing the raw materials in parts by weight;

(2) uniformly mixing the thermoplastic elastomer polymer, maleic anhydride and dicumyl peroxide, adding the mixture into a reaction type double-screw extruder preheated to 180-200 ℃, and carrying out extrusion grafting reaction at 180-200 ℃ to obtain a graft type thermoplastic elastomer polymer;

(3) adding the grafted thermoplastic elastomer polymer obtained in the step (2) into a reaction kettle at the temperature of 160-; adding the cross-linking agent, continuing stirring for 15-25 minutes, and cooling to room temperature to obtain the product.

2. A hot-melt pressure-sensitive adhesive suitable for bonding a polyolefin woven fabric to a metal plate as claimed in claim 1, wherein: the tackifying resin is selected from one or more than two of petroleum resin, terpene phenolic resin, rosin ester and rosin.

3. A hot-melt pressure-sensitive adhesive suitable for bonding a polyolefin woven fabric to a metal plate as claimed in claim 1, wherein: the plasticizer is liquid polyisobutene with the molecular weight of 500-2000.

4. A hot-melt pressure-sensitive adhesive suitable for bonding a polyolefin woven fabric to a metal plate as claimed in claim 1, wherein: the antioxidant is compounded by antioxidant 1010 and antioxidant DLTDP.

5. A hot-melt pressure-sensitive adhesive suitable for bonding a polyolefin woven fabric to a metal plate as claimed in claim 1, wherein: the cross-linking agent is liquid bisphenol A epoxy resin.